Phase-change semiconductor device and methods of manufacturing the same

ABSTRACT

In a phase-change semiconductor device and methods of manufacturing the same, an example method may include forming a metal layer pattern on a substrate, the metal layer pattern including an opening that exposes a portion of the substrate, forming an etch stop layer on the metal layer pattern, a sidewall of the opening and the exposed portion of the substrate, the etch stop layer formed with a thickness less than an upper thickness threshold, and reducing at least a portion of the etch stop layer, the reduced portion of the etch stop layer forming an electrical connection with the substrate.

PRIORITY STATEMENT

This application is a divisional of application Ser. No. 11/482,760,filed Jul. 10, 2006, which claims priority under 35 USC §119 TO KoreanPatent Application No. 2005-62487 filed on Jul. 12, 2005, the contentsof each of which are herein incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Example embodiments of the present invention relate to a semiconductordevice and methods of manufacturing the same, and more particularly, toa phase-change semiconductor memory device and methods of manufacturingthe same.

2. Description of the Related Art

Semiconductor devices such as dynamic random access memory (DRAM)devices, static random access memory (SRAM) devices, flash memorydevices, etc. may be included in various electric and/or electronicapparatuses. Semiconductor devices may generally be classified asvolatile memory devices or nonvolatile memory devices. Volatile memorydevices may lose data stored therein when a power supply is turned offor drops below a voltage threshold, whereas nonvolatile memory devicesmay maintain data stored therein even after a power supply is turned offor drops below a voltage threshold. In an example, nonvolatile memorydevices such as flash memory devices may be employed within digitalcameras, MP3 players, cellular phones, etc., to maintain data integritywithout a constant power supply.

Conventional flash memory devices may have longer read access andprogramming times as compared to random access memory (RAM) devices. Aferroelectric random access memory (FRAM) device, a magnetic randomaccess memory (MRAM) device, a phase-change random access memory (PRAM)device, etc. may be employed which may have faster read access andprogramming times than flash memory devices.

Conventional PRAM devices may include a phase-change material which mayalternate between a crystalline structure and an amorphous structure inaccordance with heat generated by electrical power or current. Anexample of conventional phase-change materials which may be included ina PRAM device may include a chalcogenide alloy. The chalcogenide alloymay include a mixture of germanium (Ge), antimony (Sb) and tellurium(Te), and may be referred to as a “GST”.

Conventional PRAM devices may include a phase-change layer configured toreceive an electric current. A crystalline phase of the phase-changematerial may be adjusted based on a current level and a duration of thereceived electric current. Conventional PRAM devices may have aresistance which may vary based on a phase of the phase-change material,such that the crystalline and amorphous phases are each associated withdifferent resistances. For example, the phase-change material in thecrystalline phase may have a lower resistance than the phase-changematerial in the amorphous phase. The difference in the resistances ofthe crystalline and amorphous phases of the phase-change material mayallow the PRAM device to be associated with one of a first logic level(e.g., a higher logic level) and a second logic level (e.g., a lowerlogic level). Examples of PRAM devices are well known in the art.

FIG. 1 is a cross-sectional view illustrating a phase change memory cellof a conventional PRAM device.

Referring to FIG. 1, the PRAM device may include a semiconductorsubstrate 10, an insulating interlayer pattern 11 formed on thesemiconductor substrate 10, a contact plug 14 formed within theinsulating interlayer pattern 11, a first insulation layer pattern 20 aformed on the insulating interlayer pattern 11, a metal layer pattern 30a formed within the first insulation layer pattern 20 a, a secondinsulation layer pattern 34 b formed on the first insulation layerpattern 20 a, a contact electrode 40 a formed within the secondinsulation layer pattern 34 b, a phase-change layer pattern 44 a formedon the second insulation layer pattern 34 b, an upper electrode 48 aformed on the phase-change layer pattern 44 a and a third insulationlayer pattern 52 a formed on the upper electrode 48 a.

Referring to FIG. 1, the contact plug 14 may contact an impurity region(not shown) of the semiconductor substrate 10. The metal layer pattern30 a may contact the contact plug 14. The metal layer pattern 30 a mayelectrically connect the contact electrode 40 a to the contact plug 14.A spacer S may be formed within the second insulation layer pattern 34 bto surround the contact electrode 40 a.

Referring to FIG. 1, the metal layer pattern 30 a may be formed by adamascene process such that a void V or a seam may be generated in themetal layer pattern 30 a. The void V may be generated below the contactelectrode 40 a and/or the phase-change layer pattern 44 a and may becharacterized by a higher electrical resistance than other portions ofthe metal layer pattern 30 a. The void V may at least partially isolatethe contact electrode 40 a from the metal layer pattern 30 a.

Referring to FIG. 1, the metal layer pattern 30 a may alternatively beformed by a dry etching process. In conventional dry etching processes,a hard mask pattern (not shown) may be formed on the metal layer 30 a.The metal layer 30 a may be dry-etched using the hard mask pattern as anetching mask. The dry etching process may reduce an occurrence of thevoid V in conventional PRAM devices.

Referring to FIG. 1, while the dry etching process may reduce anoccurrence of voids, various problems may be associated with theabove-described dry etching process. For example, the hard mask pattern(not shown) may remain on the metal layer pattern 30 a with a thicknessgreater than about 3,000 Åafter the dry etching process. Thus, if thecontact electrode 40 a is formed through the hard mask pattern and thesecond insulation layer pattern 34 b, the contact electrode 40 a may notbe formed with a desired resistance. The hard mask pattern and thesecond insulation layer pattern 34 b, which may have uniformthicknesses, may thereby not be formed. The contact electrode 40 a maynot be uniformly formed at a given height through the hard mask patternand the second insulation layer pattern 34 b. Furthermore, a contacthole for forming the contact electrode 40 a may not be formed throughthe hard mask pattern and the second insulation layer pattern 34 b withhigher levels of accuracy. The spacer S may also not be formed throughthe hard mask pattern and the second insulation layer pattern 34 b.Accordingly, it may be more difficult to control an electrical currentthrough the contact electrode 40 a, which may degrade an operationalperformance of conventional PRAM devices.

SUMMARY OF THE INVENTION

An example embodiment of the present invention is directed to a methodof manufacturing a phase-change semiconductor device, including forminga metal layer pattern on a substrate, the metal layer pattern includingan opening that exposes a portion of the substrate, forming an etch stoplayer on the metal layer pattern, a sidewall of the opening and theexposed portion of the substrate, the etch stop layer formed with athickness less than an upper thickness threshold, and reducing at leasta portion of the etch stop layer, the reduced portion of the etch stoplayer forming an electrical connection with the substrate.

Another example embodiment of the present invention is directed to amethod of manufacturing a phase-change semiconductor device, includingforming a metal layer on a substrate, forming an etch stop layer on themetal layer, the etch stop layer having a thickness less than an upperthickness threshold, forming a photoresist pattern on the etch stoplayer, etching the etch stop layer and the metal layer using thephotoresist pattern to form an etch stop layer pattern and a metal layerpattern on the substrate and to form an opening exposing a portion ofthe substrate, and reducing the photoresist pattern.

Another example embodiment of the present invention is directed to aphase-change semiconductor device, including a substrate, a metal layerpattern on the substrate, the metal layer pattern including an openingthat exposes a portion of the substrate, an etch stop layer formed onthe metal layer pattern, the etch stop layer formed with a thicknessless than an upper thickness threshold and a conductive path formed inan opening in the etch stop layer and the metal layer pattern, theconductive path providing an electrical connection to the substrate.

Example embodiments of the present invention provide a method ofmanufacturing a phase-change semiconductor device including a contactelectrode having a uniform resistance.

Another example embodiment of the present invention is directed to amethod of manufacturing a phase-change semiconductor device, includingforming a metal layer pattern on a substrate. The metal layer patternmay include an opening that exposes a portion of the substrate. An etchstop layer may be formed on the metal layer pattern, a sidewall of theopening and the exposed portion of the substrate, and then an oxidelayer pattern may be formed to at least partially fill the opening.After an insulation layer is formed on the etch stop layer and the oxidelayer pattern, a contact hole may be formed through the insulation layerand the etch stop layer to expose a portion of the metal layer pattern.A contact electrode may be formed to at least partially fill the contacthole. After a phase-change layer is formed on the insulation layer andthe contact electrode, an upper electrode layer may be formed on thephase-change layer. The upper electrode layer and the phase-change layermay be successively patterned using a mask pattern. As a result, thephase-change semiconductor device including the contact electrode havinga uniform resistance may be obtained.

In another example embodiment of the present invention, the metal layerpattern may be formed by forming a metal layer on the substrate, byforming a photoresist pattern on the metal layer, by partially removingthe metal layer using the photoresist pattern as an etching mask, and byremoving the photoresist pattern.

In another example embodiment of the present invention, the etch stoplayer may be formed using silicon nitride, silicon oxynitride orsilicon-rich silicon oxide that has a content of silicon substantiallygreater than that of the oxide layer pattern. The etch stop layer mayhave a thickness of about 100 Åto about 2,000 Å.

In another example embodiment of the present invention, the oxide layerpattern may be formed by forming an oxide layer to at least partiallyfill the opening and to cover the etch stop layer and by performing aplanarization process on the oxide layer until an upper face of the etchstop layer is exposed.

In another example embodiment of the present invention, a spacer may beformed on a sidewall of the contact hole.

Another example embodiment of the present invention is directed to amethod of manufacturing a phase-change semiconductor device, includingforming a metal layer on a substrate. An etch stop layer may be formedon the metal layer, and then a photoresist pattern may be formed on theetch stop layer. The etch stop layer and the metal layer may besuccessively etched using the photoresist pattern to form an etch stoplayer pattern and a metal layer pattern on the substrate, and to form anopening exposing a portion of the substrate. An oxide layer pattern maybe formed to at least partially fill the opening. After an insulationlayer is formed on the etch stop layer pattern and the oxide layerpattern, a contact hole may be formed through the insulation layer andthe etch stop layer. The contact hole may expose a portion of the metallayer pattern. A contact electrode may be formed to at least partiallyfill the contact hole. The contact electrode may be electricallyconnected to the metal layer pattern. After a phase-change layer isformed on the insulation layer, an upper electrode layer may be formedon the phase-change layer. The upper electrode layer and thephase-change layer may be successively patterned using a mask pattern.As a result, the phase-change semiconductor device including the contactelectrode having a uniform resistance may be obtained.

In another example embodiment of the present invention, a metal layerpattern may be formed by etching a metal layer using a photoresistpattern, and then an etch stop layer having a uniform thickness isformed on the metal layer pattern. Thus, a contact electrode having adesired height may be obtained. A thickness of an insulation layersuccessively formed on the etch stop layer may be easily controlled, andthe height of the contact electrode may be adjusted. As a result, thecontact electrode having a desired electrical resistance may beobtained. Therefore, a phase-change semiconductor device including thecontact electrode having a uniform resistance may have enhancedelectrical characteristics in programming and erasing operations.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a furtherunderstanding of the invention, and are incorporated in and constitute apart of this specification. The drawings illustrate example embodimentsof the present invention and, together with the description, serve toexplain principles of the present invention.

FIG. 1 is a cross-sectional view illustrating a phase change memory cellof a conventional PRAM device.

FIG. 2 is a cross-sectional view illustrating a phase-changesemiconductor device according to an example embodiment of the presentinvention.

FIGS. 3 to 8 are cross-sectional views illustrating a method ofmanufacturing the phase-change semiconductor device illustrated in FIG.2.

FIGS. 9 to 16 are cross-sectional views illustrating a method ofmanufacturing a phase-change semiconductor device according to anotherexample embodiment of the present invention.

DESCRIPTION OF EXAMPLE EMBODIMENTS OF THE PRESENT INVENTION

Example embodiments of the present invention are described more fullyhereinafter with reference to the accompanying drawings, in whichexample embodiments of the present invention are shown. The presentinvention may, however, be embodied in many different forms and shouldnot be construed as limited to the example embodiments set forth herein.Rather, these example embodiments are provided so that this disclosurewill be thorough and complete, and will fully convey the scope of thepresent invention to those skilled in the art. In the drawings, thesizes and relative sizes of layers and regions may be exaggerated forclarity.

It will be understood that when an element or layer is referred to asbeing “on”, “connected to” or “coupled to” another element or layer, itcan be directly on, connected or coupled to the other element or layeror intervening elements or layers may be present. In contrast, when anelement is referred to as being “directly on,” “directly connected to”or “directly coupled to” another element or layer, there are nointervening elements or layers present. Like reference numerals refer tolike elements throughout. As used herein, the term “and/or” includes anyand all combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, third etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer orsection from another region, layer or section. Thus, a first element,component, region, layer or section discussed below could be termed asecond element, component, region, layer or section without departingfrom the teachings of the present invention.

Spatially relative terms, such as “beneath”, “below”, “lower”, “above”,“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the example term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particularexample embodiments only and is not intended to be limiting of thepresent invention. As used herein, the singular forms “a”, “an” and“the” are intended to include the plural forms as well, unless thecontext clearly indicates otherwise. It will be further understood thatthe terms “comprises” and/or “comprising,” when used in thisspecification, specify the presence of stated features, integers, steps,operations, elements, and/or components, but do not preclude thepresence or addition of one or more other features, integers, steps,operations, elements, components, and/or groups thereof.

Example embodiments of the present invention are described herein withreference to cross-section illustrations that are schematicillustrations of idealized embodiments (and intermediate structures) ofthe present invention. As such, variations from the shapes of theillustrations as a result, for example, of manufacturing techniquesand/or tolerances, are to be expected. Thus, example embodiments of thepresent invention should not be construed as limited to the particularshapes of regions illustrated herein but are to include deviations inshapes that result, for example, from manufacturing. For example, animplanted region illustrated as a rectangle may have rounded or curvedfeatures and/or a gradient of implant concentration at its edges ratherthan a binary change from implanted to non-implanted region. Likewise, aburied region formed by implantation may result in some implantation inthe region between the buried region and the surface through which theimplantation takes place. Thus, the regions illustrated in the figuresare schematic in nature and their shapes are not intended to illustratethe actual shape of a region of a device and are not intended to limitthe scope of the present invention.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which the present invention belongs. Itwill be further understood that terms, such as those defined in commonlyused dictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

FIG. 2 is a cross-sectional view illustrating a phase-changesemiconductor device according to an example embodiment of the presentinvention.

In the example embodiment of FIG. 2, the phase-change semiconductordevice may include a semiconductor substrate 100, a first insulationlayer 110 formed on the semiconductor substrate 100, a metal layerpattern 120 a formed on the first insulation layer 110, an etch stoplayer 130 formed on an upper face and a sidewall of the metal layerpattern 120 a and the first insulation layer 110, a second insulationlayer pattern 140 a formed between adjacent metal layer patterns 120 a,a third insulation layer pattern 150 a formed on the metal layer pattern120 a, a contact electrode 160 formed through the etch stop layer 130and the third insulation layer pattern 150, a phase-change layer pattern170 a formed on the third insulation layer pattern 150 a, and an upperelectrode 180 a formed on the phase-change layer pattern 170 a.

In the example embodiment of FIG. 2, the first insulation layer 110 maybe formed on the semiconductor substrate 100 with or without anintervening layer or layers. The first insulation layer 110 may includea contact plug (not shown) electrically connected to the semiconductorsubstrate 100. In an example, the first insulation layer 110 may includean oxide (e.g., boro-phosphor silicate glass (BPSG), phosphor silicateglass (PSG), undoped silicate glass (USG), spin-on glass (SOG),tetraethyl orthosilicate (TEOS), etc.).

In the example embodiment of FIG. 2, the metal layer pattern 120 a maybe formed on the first insulation layer 110 and may be electricallyconnected to the contact plug (not shown). In an example, the metallayer pattern 120 a may include a conductive material (e.g., one or moreof titanium (Ti), aluminum (Al), tungsten (W), tantalum (Ta), tantalumnitride (TaN), etc.).

In the example embodiment of FIG. 2, the etch stop layer 130 may beformed on the upper face and the sidewall of the metal layer pattern 120a and on the first insulation layer 110. The etch stop layer 130 mayinclude a contact hole in which the contact electrode 160 may be formed.In an example, the etch stop layer 130 may include silicon nitride,silicon oxynitride and/or silicon-rich silicon oxide. In a furtherexample, the silicon-rich silicon oxide may have a content level ofsilicon greater than that of other silicon oxides.

In the example embodiment of FIG. 2, the etch stop layer 130 may be usedas an etching and/or polishing stopper in an etching process and/or apolishing process for forming the second insulation layer pattern 140 a.The etch stop layer 130 may not function as an etching mask in a processof forming the second insulation layer pattern 140 a. In an example, theetch stop layer 130 may have a thickness less than or equal to an upperthickness threshold (e.g., about 3,000 Å), which may allow greatercontrol of a thickness of the third insulation layer pattern 150 a. In afurther example, the etch stop layer 130 may have a thickness betweenabout 100 Å and about 2,000 Å. In yet another example, the thickness ofthe etch stop layer 130 may be in a range between about 200 Åand about1,500 Å.

In the example embodiment of FIG. 2, if the etch stop layer 130 has athickness which is less than or equal to the upper thickness threshold(e.g., about 3,000 Å), the contact electrode 160 may achieve a uniformresistance and/or height at given respective levels (e.g., levelssufficient for deployment in a PRAM). If the uniform resistance and/orheight of the contact electrode 160 are greater than a resistancethreshold and/or a height threshold, a current delay of current flowingthrough the contact electrode 160 may be generated.

In the example embodiment of FIG. 2, the etch stop layer 130 may be usedfor forming the contact electrode 160 at a uniform height so as toenhance electrical characteristics of the phase-change semiconductordevice, for example by improving a performance of programming and/orerasing operations of the phase-change semiconductor device.

In another example embodiment of the present invention, referring toFIG. 2, the phase-change semiconductor device may include an ohmiccontact layer (not shown) formed on the metal layer pattern 120 a. In anexample, the ohmic contact layer may include a conductive material(e.g., a nitrogen-containing conductive material, a metal, a metalsilicide, etc.). Examples of the nitrogen-containing conductive materialmay include one or more of titanium nitride, tantalum nitride,molybdenum nitride, titanium silicon nitride, titanium aluminum nitride,titanium boron nitride, zirconium silicon nitride, tungsten siliconnitride, tungsten boron nitride, zirconium aluminum nitride, molybdenumsilicon nitride, molybdenum aluminum nitride, tantalum silicon nitride,tantalum aluminum nitride, titanium oxynitride, titanium aluminumoxynitride, tungsten oxynitride, tantalum oxynitride, etc.

In the example embodiment of FIG. 2, the third insulation layer pattern150 a may be formed on the etch stop layer 130 positioned on the metallayer pattern 120 a. The third insulation layer pattern 150 a mayinclude the contact hole (not shown) in which the contact electrode 160may be formed. The contact hole may be formed through the thirdinsulation layer pattern 150 a and the etch stop layer 130 so as toexpose a portion of the metal layer pattern 120 a. The third insulationlayer pattern 150 a may isolate the phase-change layer pattern 170 afrom the metal layer pattern 120 a. The third insulation layer pattern150 a may define a region in which the contact electrode 160 may beformed.

In the example embodiment of FIG. 2, the phase-change semiconductordevice may further include a spacer (not shown) formed on a sidewall ofthe contact hole. For example, the spacer may be included if a processmargin is insufficient in a photolithography process for forming thecontact hole through the third insulation layer pattern 150 a and theetch stop layer 130. In a further example, the contact electrode 160 mayhave a diameter smaller than that of the contact hole.

In the example embodiment of FIG. 2, the contact electrode 160 may beformed so as to at least partially fill the contact hole. The contactelectrode 160 may be electrically connected to the metal layer pattern120 a. In an example, the height of the contact electrode 160 may besubstantially equal to a sum of thicknesses of the etch stop layer 130and the third insulation layer pattern 150 a. The contact electrode 160may function as a passage for current flowing from the metal layerpattern 120 a to the phase-change layer pattern 170 a. The contactelectrode 160 may have a smaller diameter. Thereby, a relatively largeresistance may be generated between the contact electrode 160 and thephase-change layer pattern 170 a even if a relatively small currentflows through the contact electrode 160. In another example, the contactelectrode 160 may correspond to a lower electrode.

In the example embodiment of FIG. 2, the phase-change layer pattern 170a may be formed on the contact electrode 160 and the third insulationlayer pattern 150 a. In an example, the phase-change layer pattern 170 amay include a chalcogenide alloy. Examples of chalcogenide alloys mayinclude one or more of germanium-antimony-tellurium (GST),arsenic-antimony-tellurium, tin-antimony-tellurium,tin-indium-tellurium, tin-indium-antimony-tellurium,arsenic-germanium-antimony-tellurium, an element in Group5A-antimony-tellurium, an element in Group 6A-antimony-tellurium, theelement in Group 5A-antimony-selenium, the element in Group6A-antimony-selenium, etc. Examples of Group 5A elements may include oneor more of tantalum, niobium, vanadium, etc. Examples of Group 6Aelements may include one or more of tungsten, molybdenum, chromium, etc.

In the example embodiment of FIG. 2, the upper electrode 180 a may beformed on the phase-change layer pattern 170 a. The upper electrode 180a may include a conductive material. For example, the upper electrode180 a may include substantially the same conductive material as that ofthe contact electrode 160.

In another example embodiment of the present invention, referring toFIG. 2, the phase-change semiconductor device may include the etch stoplayer 130 with a thickness below an upper thickness threshold (e.g.,about 3,000 Å) such that the contact electrode 160 may be formed havinga desired, uniform resistance and/or a desired, uniform height. Thus,the phase-change semiconductor device may have enhanced electricalcharacteristics such as improved performance associated with programmingand/or erasing operations.

FIGS. 3 to 8 are cross-sectional views illustrating a method ofmanufacturing the phase-change semiconductor device illustrated in FIG.2.

In the example embodiment of FIG. 3, a first insulation layer 110, ametal layer 120 and a first photoresist pattern 122 may formed on asemiconductor substrate 100. The first insulation layer 110 may beformed on the semiconductor substrate 100. A lower structure (not shown)may be formed on the semiconductor substrate 100. For example, the lowerstructure may include an isolation layer, a contact region, atransistor, a bit line and/or a contact plug. The first insulation layer110 may be formed with an oxide including one or more of BPSG, PSG, USG,SOG, TEOS, etc. In an example, the first insulation layer 110 may beformed by a chemical vapor deposition (CVD) process, a plasmaenhanced-chemical vapor deposition (PE-CVD) process, an atomic layerdeposition (ALD) process and/or a high density plasma-chemical vapordeposition (HDP-CVD) process.

In the example embodiment of FIG. 3, the metal layer 120 may be formedon the first insulation layer 110. The metal layer 120 may be formedwith a conductive material, for example one or more of tungsten,aluminum, copper, titanium, tantalum, tantalum nitride, etc. In anexample, the metal layer 120 may be formed by a PE-CVD process and/or asputtering process.

In the example embodiment of FIG. 3, a photoresist film may be formed onthe metal layer 120 by coating the metal layer 120 with a photoresistcomposition. An exposure process and a developing process may beperformed on the photoresist film to form the first photoresist pattern122 on the metal layer 120. A thickness of the first photoresist pattern122 may vary in accordance with a thickness of the metal layer 120.

In the example embodiment of FIG. 4, the metal layer pattern 120 a andthe etch stop layer 130 may be formed on the first insulation layer 110.The metal layer 120 may be dry etched using the first photoresistpattern 122 as an etching mask to form the metal layer pattern 120 a onthe first insulation layer 100. The metal layer pattern 120 a mayinclude an opening exposing a portion of the first insulation layer 110.In an example, the first photoresist pattern 122 may be removed by anaching process and/or a stripping process.

In the example embodiment of FIG. 4, the etch stop layer 130 may beformed on an upper face and a sidewall of the metal layer pattern 120 aand the exposed portion of the first insulation layer 110. In anexample, the etch stop layer 130 may be formed with one or more ofsilicon nitride, silicon oxynitride and/or silicon-rich silicon oxide.In a further example, the silicon-rich silicon oxide may include ahigher content of silicon than that of other silicon oxides.

In the example embodiment of FIG. 4, the etch stop layer 130 mayfunction as an etching stopper in an etching process and/or a polishingstopper in a polishing process for forming the second insulation layerpattern 140 a (e.g., see FIG. 5) in the opening 124. In an example, theetch stop layer 130 may not function as an etching mask in the etchingprocess and/or the polishing process. In a further example, the etchstop layer 130 may have a thickness below the upper thickness threshold(e.g., about 3,000 Å) such that a thickness of a third insulation layer150 (e.g., see FIG. 6) may be controlled with greater precision. In afurther example, the etch stop layer 130 may have a thickness betweenabout 100 Åand about 2,000 Å. In yet another example, the etch stoplayer 130 may have a thickness between about 200 Åand about 1,500 Å.

In the example embodiment of FIG. 4, the etch stop layer 130 may have arelatively uniform thickness. Thereby, the contact electrode 160 (e.g.,see FIG. 7) formed through the etch stop layer 130 and the thirdinsulation layer 150 may have a relatively uniform height. Thus,electrical characteristics, for example, performance associated withprogramming and/or erasing operations of the phase-change semiconductordevice, may be improved.

In the example embodiment of FIG. 5, the second insulation layer pattern140 a may be formed on the etch stop layer to at least partially fillthe opening 124. The second insulation layer covering (e.g., at leastpartially) the metal layer pattern 120 a may be formed on the etch stoplayer 130 to at least partially fill the opening 124. In an example, thesecond insulation layer may include an oxide with one or more of BPSG,PSG, USG, SOG, TEOS, etc. In another example, the second insulationlayer may be formed by a process substantially the same as that employedfor forming the first insulation layer 110.

In the example embodiment of FIG. 5, the second insulation layer may bepartially reduced (e.g., removed) until the etch stop layer 130 formedon the metal layer pattern 120 a may be exposed so as to form the secondinsulation layer pattern 140 a. In an example, the second insulationlayer may be at least partially reduced (e.g., removed) by a chemicalmechanical polishing (CMP) process, an etch back process or acombination process of CMP and etch back.

In the example embodiment of FIG. 6, a preliminary third insulationlayer may be formed on the etch stop layer 130 and the second insulationlayer pattern 140 a. A second photoresist pattern (not shown) may beformed on the preliminary third insulation layer. The preliminary thirdinsulation layer and the etch stop layer 130 may be partially reduced(e.g., removed) using the second photoresist pattern as an etching maskto form a contact hole 154 exposing a portion of the metal layer pattern120 a. The preliminary third insulation layer and the etch stop layer130 may be partially reduced (e.g., removed) by a dry etching process.Thereby, the third insulation layer 150 including the contact hole 154may be formed on the etch stop layer 130 and the second insulation layerpattern 140 a. In an example, the second photoresist pattern may bereduced (e.g., removed) by an ashing process and/or a stripping process.

In the example embodiment of FIG. 7, the contact electrode 160 may beformed through the etch stop layer 130 and the third insulation layer150 to at least partially fill the contact hole 154. The contactelectrode 160 may contact the metal layer pattern 120 a.

In the example embodiment of FIG. 7, a conductive layer may be formed onthe third insulation layer 150 to at least partially fill the contacthole 154. The conductive layer may be partially reduced (e.g., removed)until the third insulation layer 150 may be exposed so as to form thecontact electrode 160. In an example, the conductive layer may bepartially reduced (e.g., removed) by a CMP process, an etch back processor a combination process of CMP and etch back. Thus, the contactelectrode 160 electrically connected to the metal layer pattern 120 amay be formed in the contact hole 154. In an example, the conductivelayer may be formed using a conductive material including one or more oftantalum, copper, tungsten, titanium, aluminum or a nitride thereof. Inanother example, the conductive layer may be formed with a CVD process,a sputtering process and/or an ALD process.

In the example embodiment of FIG. 7, the contact electrode 160 may havea relatively high aspect ratio. Thus, an electric current received fromthe metal layer pattern 120 a may flow through a small cross-section ofthe contact electrode 160 such that a lower amount of electric currentmay generate a higher amount of heat. For example, the generated heatmay be sufficient to trigger a change of the phase change layer 170(e.g., to/from a crystalline phase) (e.g., see FIG. 8).

In the example embodiment of FIG. 8, the phase-change layer 170 may beformed on the third insulation layer 150 including the contact electrode160. In an example, the phase-change layer 170 may be formed with achalcogenide alloy by a sputtering process. Examples of the chalcogenidealloy may include one or more of germanium-antimony-tellurium (GST),arsenic-antimony-tellurium, tin-antimony-tellurium,tin-indium-tellurium, tin-indium-antimony-tellurium,arsenic-germanium-antimony-tellurium, an element in Group5A-antimony-tellurium, an element in Group 6A-antimony-tellurium, theelement in Group 5A-antimony-selenium, the element in Group6A-antimony-selenium, etc. Examples of Group 5A elements may includetantalum, niobium, vanadium, etc. Examples Group 6A elements may includetungsten, molybdenum, chromium, etc.

In the example embodiment of FIG. 8, an upper electrode layer 180 may beformed on the phase-change layer 170 with one or more of a CVD process,a physical vapor deposition (PVD) process and an ALD process. In anexample, the upper electrode layer 180 may be formed with a conductivematerial including one or more of a nitrogen-containing conductivematerial, a metal and a metal silicide. Examples of thenitrogen-containing conductive material may include one or more oftitanium nitride, tantalum nitride, molybdenum nitride, titanium siliconnitride, titanium aluminum nitride, titanium boron nitride, zirconiumsilicon nitride, tungsten silicon nitride, tungsten boron nitride,zirconium aluminum nitride, molybdenum silicon nitride, molybdenumaluminum nitride, tantalum silicon nitride, tantalum aluminum nitride,titanium oxynitride, titanium aluminum oxynitride, tungsten oxynitride,tantalum oxynitride, etc.

In the example embodiment of FIG. 8, an etching mask (not shown) may beformed on the upper electrode layer 180. The upper electrode layer 180,the phase-change layer 170, and the third insulation layer 150 may bepatterned to form an upper electrode 180 a, a phase-change layer pattern170 a and a third insulation layer pattern 150 a on the etch stop layer130 positioned over the metal layer pattern 120 a as illustrated in FIG.2. Accordingly, after the patterning, a phase-change semiconductordevice may be achieved.

In the example embodiment of FIGS. 2 and 8, the phase-changesemiconductor device may include the contact electrode 160 formedthrough the third insulation layer pattern 150 a, the phase-change layerpattern 170 a formed on the contact electrode 160 and the thirdinsulation layer pattern 150 a, and the upper electrode 180 a formed onthe phase-change layer pattern 170 a. Further, a fourth insulation layermay be formed on the upper electrode 180 a so as to isolate the upperelectrode 180 a from an adjacent upper electrode.

FIGS. 9 to 16 are cross-sectional views illustrating a method ofmanufacturing a phase-change semiconductor device according to anotherexample embodiment of the present invention.

In the example embodiment of FIG. 9, an isolation layer 332 may beformed at an upper portion of a semiconductor substrate 330. Theisolation layer 332 may be formed by an isolation process such as ashallow trench isolation (STI) process. The isolation layer 332 maydivide the semiconductor substrate 330 into an active region and a fieldregion.

In the example embodiment of FIG. 9, an insulation layer and aconductive layer may be formed on the semiconductor substrate 330. In anexample, the insulation layer may be formed with one or more of oxide,metal oxide, metal oxynitride, etc. In another example, the insulationlayer may be formed by an ALD process.

In the example embodiment of FIG. 9, the conductive layer may be formedwith one or more of polysilicon doped with impurities (e.g., metal,conductive metal nitride, metal silicide, etc). A gate conductive layer336 having a multi-layer structure may be formed on the semiconductorsubstrate 330 to enhance electrical characteristics of the phase-changesemiconductor device. In an example, the conductive layer may have amulti-layer structure with both a metal layer and a metal nitride layer.

In the example embodiment of FIG. 9, the conductive layer and theinsulation layer may be patterned to form a gate pattern 338 including agate insulation layer 334 and the gate conductive layer 336 in theactive region of the semiconductor substrate 330. A hard mask pattern(not shown) and/or a photoresist pattern (not shown) may be formed onthe conductive layer. The conductive layer and the insulation layer maybe etched using the hard mask pattern and/or the photoresist pattern. Ifthe hard mask pattern is formed on the conductive layer, the gatepattern 338 may include the hard mask pattern formed on the gateconductive layer 336.

In the example embodiment of FIG. 9, a first ion implantation processmay be performed on the semiconductor substrate 330 using the gatepattern 338 as an ion implantation mask to form lightly doped regions atportions of the semiconductor substrate 330 adjacent to the gate pattern338.

In the example embodiment of FIG. 9, a gate spacer 340 may be formed ona sidewall of the gate pattern 338. A second ion implantation processmay be performed on the semiconductor substrate 330 using the gatepattern 338 and the gate spacer 340 as ion implantation masks to formheavily doped regions (e.g., more heavily than the lightly dopedregions) at portions of the semiconductor substrate 330 adjacent to thegate pattern 330. Source/drain regions 342 having lightly doped drain(LDD) structures may be formed at the portions of the semiconductorsubstrate 330. A bit line (not shown) may be formed over the gatepattern 38.

In the example embodiment of FIG. 10, a first insulating interlayer maybe formed on the semiconductor substrate 330 including the gate pattern338 thereon. The first insulation interlayer may be patterned to form afirst insulation interlayer pattern 210 a including openings 345exposing the source/drain regions 342. The openings 345 may be at leastpartially filled with a conductive material such as doped polysilicon,metal, etc. Contact pads 346 may thereby be formed on the semiconductorsubstrate 330 to at least partially fill the openings 345.

In the example embodiment of FIG. 10, one or more of the contact pads346 may be formed by a deposition process and/or by a planarizationprocess. Examples of the planarization process may include a CMPprocess, an etch back process or a combination process of CMP and etchback. The contact pads 346 may include a first plug formed betweenadjacent gate patterns 338 and a second plug formed on the first plug.

In the example embodiment of FIG. 11, a metal layer 220 may be formed onthe first insulating interlayer pattern 210 a and the contact pads 346.In an example, the metal layer 220 may be formed using a conductivematerial including one or more of tungsten, aluminum, copper, titanium,tantalum, tantalum nitride, etc. In another example, the metal layer 220may be formed by a PE-CVD process and/or a sputtering process.

In the example embodiment of FIG. 11, an etch stop layer 230 may beformed on the metal layer 220. The etch stop layer 230 may include oneor more of silicon nitride, silicon oxynitride and silicon-rich siliconoxide. In an example, the silicon-rich silicon oxide may have a highercontent of silicon as compared to that of other silicon oxides. A firstphotoresist pattern 232 may be formed on the etch stop layer 230.

In the example embodiment of FIG. 12, the etch stop layer 230 and themetal layer 220 may be etched using the first photoresist pattern 232 asan etching mask to form an etch stop layer pattern 230 a and a metallayer pattern 220 a on the first insulating interlayer pattern 210 a andthe contact pads 346. In an example, the etch stop layer pattern 230 aand the metal layer pattern 220 a may be formed by a dry etchingprocess. The etch stop layer 230 may be used for forming a contactelectrode 260 (e.g., see FIG. 14) having a uniform height to enhanceelectrical characteristics of the phase-change semiconductor device.Adjacent metal layer patterns 220 a may be isolated from each other withan opening exposing a portion of the first insulating interlayer pattern210 a. The first photoresist pattern 232 may be reduced (e.g., removed)by an ashing process and/or a stripping process.

In the example embodiment of FIG. 12, a second insulating interlayercovering the metal layer pattern 220 a may be formed on the etch stoplayer pattern 230 a to at least partially fill the opening. The secondinsulating interlayer may include an oxide with one or more of BPSG,PSG, USG, SOG, TEOS, etc. In an example, the second insulatinginterlayer may be formed by a CVD process, a PE-CVD process, an ALDprocess and/or an HDP-CVD process. The second insulating interlayer maybe at least partially reduced (e.g., removed) until the etch stop layerpattern 230 a may be exposed so as to form a second insulatinginterlayer pattern 240 a on the first insulating interlayer pattern 210a. In an example, the second insulating interlayer may be at leastpartially reduced (e.g., removed) by a chemical mechanical polishing(CMP) process, an etch back process or a combination process of CMP andetch back.

In the example embodiment of FIG. 12, the etch stop layer pattern 230 amay be used as a stopper in the planarization process for forming thesecond insulating interlayer pattern 240 a for at least partiallyfilling the opening. In an example, the etch stop layer pattern 230 amay not be used as an etching mask in an etching process for forming themetal layer pattern 220 a. In another example, the etch stop layerpattern 230 a may have a thickness below the upper thickness threshold(e.g., about 3,000 Å) such that a thickness of a third insulation layer250 (e.g., see FIG. 13) may be controlled with greater precision. Forexample, the etch stop layer pattern 230 a may have a thickness betweenabout 100 Åand about 2,000 Å. In a further example, the etch stop layerpattern 230 a may have a thickness between about 200 Åand about 1,500 Å.

In the example embodiment of FIG. 13, a preliminary third insulatinginterlayer may be formed on the etch stop layer pattern 230 a and thesecond insulating interlayer pattern 240 a. A second photoresist pattern(not shown) may be formed on the preliminary third insulatinginterlayer. The preliminary third insulating interlayer and the etchstop layer pattern 230 a may be dry etched using the second photoresistpattern as an etching mask to form a contact hole 254 exposing a portionof the metal layer pattern 220 a. A third insulating interlayer 250including the contact hole 254 may be formed on the etch stop layerpattern 230 a and the second insulating interlayer pattern 240 a. Thesecond photoresist pattern may be reduced (e.g., removed) by an ashingprocess and/or a stripping process.

In the example embodiment of FIG. 14, a spacer 252 and a contactelectrode 260 may be formed through the etch stop layer pattern 230 aand the third insulating interlayer 250 to at least partially fill thecontact hole 254. The contact electrode 260 may contact the metal layerpattern 220 a. An insulation layer may be formed on the third insulatinginterlayer 250 and the insulation layer may be at least partiallyreduced (e.g., removed) by an etch back process to form the spacer 252on a sidewall of the contact hole 254. After a formation of the spacer252, a conductive layer may be formed on the third insulating interlayer250 to at least partially fill the contact hole 254. The conductivelayer may be reduced (e.g., partially removed) until an upper face ofthe third insulating interlayer 250 may be exposed. In an example, theconductive layer may be reduced (e.g., partially removed) by a CMPprocess, an etch back process or a combination process of CMP and etchback. Accordingly, the contact electrode 260 may be formed to at leastpartially fill the contact hole 254. The spacer 252 may surround thecontact electrode 260. In an example, the contact electrode 260 mayinclude a conductive material substantially the same as the conductivematerial included within the contact electrode 160 described above withreference to the example embodiment of FIG. 7.

In the example embodiment of FIG. 15, a phase-change layer 270 may beformed on the third insulating interlayer 250 including the contactelectrode 260 surrounded by the spacer 252. In an example, thephase-change layer 270 may include a chalcogenide alloy by a sputteringprocess. Examples of the chalcogenide alloy have been described abovewith respect to the example embodiment of FIG. 8, and therefore afurther detailed description of chalcogenide alloy examples have beenomitted for the sake of brevity.

In the example embodiment of FIG. 15, an upper electrode layer 280 maybe formed on the phase-change layer 270 by a CVD process, a PVD processand/or an ALD process. In an example, the upper electrode layer 280 maybe formed with a conductive material including one or more of anitrogen-containing conductive material, metal and metal silicide.Examples of the conductive material have been described above withrespect to the example embodiment of FIG. 8, and therefore a furtherdetailed description of conductive material examples have been omittedfor the sake of brevity.

In the example embodiment of FIG. 16, an etching mask (not shown) may beformed on the upper electrode layer 280. The upper electrode layer 280,the phase-change layer 270, and the third insulating interlayer 250 maybe patterned using the etching mask to form a upper electrode 280 a, aphase-change layer pattern 270 a and a third insulating interlayerpattern 250 a on the etch stop layer pattern 230 a to form aphase-change memory cell.

In the example embodiment of FIG. 16, the phase-change memory cell mayinclude the contact electrode 260 formed through the third insulatinginterlayer pattern 250 a, the spacer 252 surrounding the contactelectrode 260, the phase-change layer pattern 270 a formed on thecontact electrode 260 and the third insulating interlayer pattern 250 a,and the upper electrode 280 a formed on the phase-change layer pattern270 a. Additionally, a fourth insulation layer may be formed on theupper electrode 280 a to electrically isolate adjacent upper electrodes280 a from each other.

In another example embodiment of the present invention, a metal layerpattern may be formed by etching a metal layer using a photoresistpattern. An etch stop layer (e.g., with a thickness below an upperthickness threshold) may be formed on the metal layer pattern. The etchstop layer may be used to attain a contact electrode having a desiredheight. A thickness of an insulation layer formed on the etch stop layermay be controlled with higher levels of precision, and a height of thecontact electrode may be adjusted. The contact electrode may thereby beformed with a desired electrical resistance with a uniform height,thereby improving electrical characteristics (e.g., a performance ofprogramming and/or erasing operations) of a phase-change device.

Example embodiments of the present invention being thus described, itwill be obvious that the same may be varied in many ways. For example,while the above-described example embodiments include references toparticular layer orders, it is understood that such layer arrangementsare given for example purposes only, and other example embodiments ofthe present invention may be directed to other arrangements. Forexample, additional intervening layers may be formed in other exampleembodiments of the present invention.

Further, the phase-change layers 170/270 and/or phase-change layerpatterns 170 a/270 a may be made of a transition metal oxide havingmultiple resistance states, as described above. For example, thephase-change layers 170/270 and/or phase-change layer patterns 170 a/270a may be made of at least one material selected from the groupconsisting of NiO, TiO₂, HfO, Nb₂O₅, ZnO, WO₃, and CoO or GST(Ge₂Sb₂Te₅) or PCMO(Pr_(x)Ca_(1−x)MnO₃). The phase-change layers 170/270and/or phase-change layer patterns 170 a/270 a may include a chemicalcompound including one or more elements selected from the groupconsisting of S, Se, Te, As, Sb, Ge, Sn, In and Ag.

In some example embodiments, as discussed above, the phase-change layers170/270 and/or phase-change layer patterns 170 a/270 a may includechalcogenide alloys such as germanium-antimony-tellurium (Ge—Sb—Te),arsenic-antimony-tellurium (As—Sb—Te), tin-antimony-tellurium(Sn—Sb—Te), or tin-indium-antimony-tellurium (Sn—In—Sb—Te),arsenic-germanium-antimony-tellurium (As—Ge—Sb—Te). Alternatively, thephase-change layers 170/270 and/or phase-change layer patterns 170 a/270a may include an element in Group V A-antimony-tellurium such astantalum-antimony-tellurium (Ta—Sb—Te), niobium-antimony-tellurium(Nb—Sb—Te) or vanadium-antimony-tellurium (V—Sb—Te) or an element inGroup VA-antimony-selenium such as tantalum-antimony-selenium(Ta—Sb—Se), niobium-antimony-selenium (Nb—Sb—Se) orvanadium-antimony-selenium (V—Sb—Se). Further, the data storage layermay include an element in Group VIA-antimony-tellurium such astungsten-antimony-tellurium (W—Sb—Te), molybdenum-antimony-tellurium(Mo—Sb—Te), or chrome-antimony-tellurium (Cr—Sb—Te) or an element inGroup VIA-antimony-selenium such as tungsten-antimony-selenium(W—Sb—Se), molybdenum-antimony-selenium (Mo—Sb—Se) orchrome-antimony-selenium (Cr—Sb—Se).

Although the phase-change layers 170/270 and/or phase-change layerpatterns 170 a/270 a are described above as being formed primarily ofternary phase-change chalcogenide alloys, the chalcogenide alloy of thephase-change layers 170/270 and/or phase-change layer patterns 170 a/270a could be selected from a binary phase-change chalcogenide alloy or aquaternary phase-change chalcogenide alloy. Example binary phase-changechalcogenide alloys may include one or more of Ga—Sb, In—Sb, In—Se,Sb₂—Te₃ or Ge—Te alloys; example quaternary phase-change chalcogenidealloys may include one or more of an Ag—In—Sb—Te, (Ge—Sn)—Sb—Te,Ge—Sb—(Se—Te) or Te₈₁—Ge₁₅—Sb₂—S₂ alloy, for example.

Such variations are not to be regarded as departure from the spirit andscope of example embodiments of the present invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included within the scope of the following claims.

1. A phase-change semiconductor device, comprising: a substrate; a metallayer pattern on the substrate, the metal layer pattern including anopening that exposes a portion of the substrate; an etch stop layerformed on the metal layer pattern, the etch stop layer formed with athickness less than an upper thickness threshold; and a conductive pathformed in an opening in the etch stop layer and the metal layer pattern,the conductive path providing an electrical connection to the substrate.2. The phase-change semiconductor device of claim 1, wherein the upperthickness threshold is about 3,000 Å.
 3. The phase-change semiconductordevice of claim 1, wherein the etch stop layer has a thickness betweenabout 100 Åto about 2,000 Å.
 4. The phase-change semiconductor device ofclaim 1, wherein the etch stop layer includes at least one of siliconnitride, silicon oxynitride and silicon-rich silicon oxide.
 5. A methodof manufacturing the phase-change semiconductor device of claim 1.